Sulfonamide aziridinyl compounds

ABSTRACT

SULFONAMIDE AZIRIDINYL COMPOUNDS CONTAINING ONE OR MORE AZIRIDINYL GROUPS, AND METHODS OF PRODUCING SAME. THE COMPOUNDS ARE SUITABLE FOR TREATING TEXILE MATERIALS, AS CURING AGENTS, AND FOR THE PREPARATION OF POLYMERS.

United States Patent Oflice 3,682,893 Patented Aug. 8, 1972 US. Cl. 260-239 E 6 Claims ABSTRACT OF THE DISCLOSURE Sulfonamide aziridinyl compounds containing one or more aziridinyl groups and methods of producing same. The compounds are suitable for treating textile materials, as curing agents, and for the preparation of polymers.

The present application is a divisional of application Ser. No. 460,480, filed June 1, 1965, now US. Pat. 3,520,889.

The sulfonamide compounds containing one or more azridinyl groups of the present invention may be repre sented by the generic structural formula:

N-on-cn-sm-av Ra I R4 R5 Y /C in which:

R R R R and R are each selected from the group consisting of hydrogen and alkyl containing from 1 to 4 carbon atoms; i.e. lower alkyl,

X and Y are each selected from the group consisting of hydrogen and organic groups, and X and Y taken together can form a heterocyclic ring of which the sulfon amide nitrogen in also a part, said ring having no more than 7 annular members.

Accordingly, it is an object of the present invention to provide novel sulfonamide aziridinyl compounds.

It is a further object of the present invention to provide polyf-unctional compounds containing a plurality of aziridinyl sulfonyl groups.

It is a further object of the present invention to provide a novel group of sulfonamide aziridinyl compounds having valuable properties and making them suitable for a variety of purposes.

It is a further object of the present invention to provide a method for the preparation of novel aziridinyl sulfonamide compounds.

Included among the compounds representated by Formula I are compounds of the general formula:

(II) R1 wherein R R R R and R have the meaning previously given above, and

R and R are each selected from the group consisting of hydrogen and alkyl, alkenyl, hydroxy substituted alkyl, substituted and unsubstituted monovalent mononuclear aromatic and alkyl aromatic groups.

Representative groups included in the above from which R and R may be selected are alkyl from 1 to 8 carbon atoms, alkenyl from 2 to 3 atoms, monohydroxy substituted alkyl from 1 to 6 carbon atoms, phenyl, halogen substituted phenyl, methyl substituted phenyl and the like.

Specific examples of compounds represented by the general Formula .II are listed below:

C] CH; I

CHZCHB CH5 I Hi H CHQCH;

R R R R and R have the meaning previously given above and R and R have the same meaning as R It is to be understood that R R R R and R can be the same or different.

R represents a divalent organic group selected from the group consisting of hydrocarbon and polyalkylene 5 oxide groups such as alkylene from 1 to 20 carbon atoms and polyoxyalkylene groups such as wherein m is from 1 to 50.

Specific examples of these compounds include:

R R R R and R have the meaning previously given above; wherein N- P Hrs r-N-CH9C 2NS0:CH7 H2N\I a and b are integers with a value of from 1 to 4 and C the sum of a and b is at least 3, the range 3 to 5 being preferred. s 'fi 1 r d d b th peel c examp es 0 compoun s encompasse y e NCHzCH--SOa-IYT-OHzCHz-bL-SOa?H-CHz-N above are listed below: 0 1 CH3 H H CH! H2 l CH2 CHI CH: CHr-CH CH: -CHrCHz-sOg-bE-CEHCHCHfiCHZ-iiI-SOflCHPC TN l N-GH1CHg-s0z-N NSor-CHT-CHT-N CH3 H E E2 Hz UHF-CH2 H! CH1 CH2 N'CH20H2-' s 01-N-(0mcmoncmcm-wws Oa-OH CH CH -N J: C 2 Ha 1 Hz Further mcluded under the general Formula I are com- CHPCH pounds represented by the structure:

R /NCHaCHz-SO2N N-SOzCH:CHz-N l l \C H: CHr-CH: CH1

CnH n 111 2 (1v NOH-CHSO1N z CH 5 CH Ra I I l a R4 RH CmHm N-CHg-OH SO -N N-s0,-cm-cm -N l CH2 JR-0H, HI wherein R R R R and R have the meaning given above, Further compounds that are included within the scope Z is selected from the group consisting of of the general Formula I are represented by the formula:

- 2, a 2a+1): Oxygen and sulfur (v1 wherein R1 R1 v a has a value of 1 to 20, c m and n have a value of from 1 to 4 and their sum is R, p R, equal to at least 3, the range 3 to 5 being preferred. Ra "fi R] R R 0 H R R Representative compounds coming within the scope of 0 4 5 5 5 0 the formula above follow below:

E CHPCH h R R R R dR h h w erem 4 an 5 ave t e same meaning as N CH 5 N previously given above, and CH: r- I c is an integer with a value of 1 to 5.

CH; Specific examples of compounds falling within the scope HwCH2 of the above formula are listed below:

NCH:4-CH: s Oa-N 0H: CH2 CH3 GIL-CH N on 01-1 so N---N so 011 CH' N/ CE: CH2 OH 2- 2 a z 2- 2 I N-0H,-0H,- s (h-N CHZCH on, ant-0H, E s CHPCES 5 /N-(JHZ-CHfl-sOg--N N-S0z-OHz-OI-Ir-N c 1' 41 a I N GHB CHZ SO2 N Hz 1 2 Hz (1H: OH: on, cal-0n, E f

*50 -N 1 g CHPCH l/N OH; CH; 2 N 502 0111 0111 N NMCHPCHPSOPN CHCHOHICH: H, CH-CHs-CH: 0112 11, 0111-0 2 Additional compounds coming within the scope of the present invention are represented by the general formula:

Additional compounds coming within the scope of the present invention and encompassed by the general Formula I containing three aziridinyl sulfonamide groups are represented by the structure:

C32 /CH2 N-S Or-CHz-CHg-N The novel aziridinyl sulfonamide compounds of the above type may be prepared by several methods. Generally, the most suitable method for the preparation of the compounds of the present invention is by reacting a suitable alkylene imine with appropriate unsaturated sulfonamides. The general equation for preparation of compounds in the present invention is shown below:

Reaction conditions for the preparation and isolation of the above sulfonamide compounds are selected based largely on considerations of the type of product that is desired as well as taking into account the structure of the starting materials. Preferably the reaction is carried out in the presence of an inert diluent and at moderate temperatures.

At least stoichiometric quantities of the alkylene imine are used. It has been found that an excess'of the alkylene imine starting material is desirable in order to obtain a satisfactory yield. Typical reaction conditions are illustrated in the examples which follow hereinbelow which, however, do not constitute a limitation of the invention.

Of particular interest and significance is the preparation of the diallyl aziridinyl sulfonamides which are included among the compounds of the Formula II. The reaction is carried out at moderate temperature to obtain aziridinyl sulfonamides having unsaturated terminal groups which are then available for further reaction.

Various alkylene imines are suitable for the preparation of the compounds and have the general structural formula:

wherein R R and R have the meaning previously given above. Mixtures of various alkylene imines may be used for purposes of the present invention.

Representative unsaturated sulfonamide compounds suitable as starting materials include:

Vinyl sulfonamide 'N-methyl vinyl sulfonamide N ,N-dimethyl vinyl sulfonamide N,N-diallyl vinyl sulfonamide 1,2bis(N-methyl vinyl sulfonamidoethoxy) ethane -N,N' bis(vinyl sulfonamido)-2-methyl piperazine Bis vinyl sulfonamide of 2,5-dimethyl piperazine N-phenyl vinyl sulfonamide The following examples are for the purposes of illustrating the novel sulfonamide compounds and methods of preparing same. As such, the examples are not to be considered as limiting the present invention but merelv illustrative thereof.

EXAMPLE I To a stirred solution of 4.3 parts by weight of ethylenimine in 17.5 parts of benzene, pre-cooled to 4 C., were added 12.28 parts of vinyl sulfonamide at such a rate as to maintain a temperature of 4-10 C. After the addition was completed, the mixture was allowed to warm spontaneously to 45 C., forming a solid mass. Crystallization of the solid from chloroform gave 2-(1-aziridinyl) ethane sulfonamide, I, M.P. 120 in the form of thick white needles. The product contains 27.85% aziridine, 19.08% nitrogen and 22.03% sulfur. The theoretical values for I are 28% aziridine, 18.66% nitrogen and 21.33% sulfur.

EXAMPLE II 12.1 parts by weight of N-methyl vinyl sulfonamide were added to a stirred solution of 8.6 parts of ethylenimine in 22 parts by weight of benzene with cooling at such rate as to maintain a temperature of 8-l0 C. After the mixture had warmed to room temperature, the product was stripped of excess ethylenimine at room temperature and 0.1 mm. pressure to give N-methyl-Z-(l-aziridinyl) ethane sulfonamide, II, which contained 21.6% aziridine, indicating a purity of 84.5%.

EXAMPLE I II To 8.6 parts by weight of ethylenimine were added 27 parts of N,N-dimethyl vinyl sulfonamide at 2534 C. The mixture was stirred till the heat of reaction subsided, at which time the product was distilled at 0.5 mm. pressure. The fraction boiling at 112 C. had a refractive index at 23 of 1.4780 and contained 23.8% aziridine, 16.34% nitrogen and 17.3% sulfur, corresponding to |N,N-dimethyl-2 (l-aziridinyl) ethane sulfonamide, III, for which the theoretical values are: 24.15% aziridine, 15.74% nitrogen and 17.9% sulfur.

7 EXAMPLE 1v N,N-diallyl vinyl sulfonamide, BJP. 83-87 (0.2 mm.), 11 1.4841 v( 19.2 parts by weight), was added to 4.3 parts by weight of ethylenimine at 23-43" C. and the reaction mixture was allowed to cool to room temperature. The product was distilled at 118-122 (0.7 mm.), and had a refractive index of 1.4906 at 24 C. It contained 17.4% aziridine, 12.69% nitrogen and 13.36% sulfur, corresponding to N,N-diallyl-2-(l-aziridinyl) ethane sulfonamide, IV, for which the calculated values are: 18.25% aziridine, 12.16% nitrogen and 13.9% sulfur.

EXAMPLE V The bis-2-aziridinyl ethane sulfonamide of 1,2-bis(N- methylamino ethoxy) ethane, V, was prepared by adding 38.7 parts by weight of 1,2-bis (N-methyl vinyl sulfonamidoethoxy) ethane to 12.9 parts of stirred ethylenimine at 21-29" with cooling. The mixture was stirred at room temperature until no more heat was evolved, then stripped at 25 C. and 0.1 mm. pressure. The resulting product contained 15.4% aziridine, corresponding to a purity of 81%.

EXAMPLE VI A solution of 3 parts by weight of N,N-bis (vinyl sulfonamido)-2-methyl piperazine in 22 parts of benzene was added at 19-26 to 2.76 parts of ethylenimine and the mixture was stirred at room temperature for one hour. The product was stripped of solvent and excess ethylenirnine at room temperature and 0.1 mm. pressure leaving a semi-solid which was extracted with 20 parts by weight of benzene. Evaporation of the benzene left a tacky solid which contained 22% aziridine which corresponds to a purity of 93% as bis [2-(aziridinyl) ethane sulfonamido]- 2-methyl piperazine, VI.

EXAMPLE VII The bis vinyl sulfonamide of 2,5-dimethyl piperazine parts by 'weight in 30 parts of benzene) was added at 26-36" with cooling to 6.08 parts of ethylenimine with stirring. The gel which formed after the addition was complete was dispersed by adding additional benzene and the suspension was stirred at room temperature for 3 hours. The product, bis (Z-aziridinylethane sulfonamide)- 2,5-dimethyl piperazine, VII, was obtained as a white solid by filtration and recrystallization from benzene, and melted at 134l38 C. It contained 21.8% aziridine, 15.3% nitrogen and 16.34% sulfur. The theoretical values for VII are: 22.2% aziridine, 14.71% nitrogen and 16.85% sulfur.

EXAMPLE VIII A solution of 2 parts by weight of N-phenyl vinyl s ulfonamide in 17.5 parts by weight of benzene was added with cooling to a stirred solution of 0.95 part by weight of ethylenimine in 17.5 parts of benzene at 24-28 C. The cooling bath was removed after the addition was complete and the mixture warmed spontaneously to 34 C. Stirring was continued until room temperature was attained, after which the product was stripped at room temperature and 0.1 mm. pressure to leave a soft solid which contained 14.8% aziridine corresponding to a purity of 77.5% as N-phenyl-Z-aziridinyl ethane sulfonamide, VIII.

Azirdinyl compounds of many different structures are known in the art and it has been observed that the reactivity of the known aziridinyl compounds varies widely. The novel compounds of the present invention exhibit many desirable properties including relatively low vapor pressure. In addition, the compounds are relatively stable thereby enabling purification by conventional procedures such as crystallization to obtain the compounds in good yields. The aziridine compounds of the present invention do not polymerize rapidly on standing in the absence of catalysts. However, they can enter into polymerization reactions with appropriate catalysts, and moreover, are capable of reaction with active hydrogen compounds, particularly active hydrogen containing polymers under suitable reaction conditions. It is to be understood that the term active hydrogen as used herein refers to active hydrogen as determined by the well-known Zerewitnoif method.

Among the many uses for the compounds of the present invention are as curing agents for epoxy resins, as components for therapeutic preparations and as comonomers in the preparation'of polymeric compositions. In addition, those compounds which have two or more aziridinyl groups in the terminal position, referred to as polyfunctional compounds, are particularly useful as crosslinking agents for polymers containing active hydrogen atoms. Moreover, the polyfunctional aziridines can be utilized for the shrink-proofing of woolen textile materials. To

complete the discussions of applications for the novel compounds of the present invention, it is to be noted that observations have indicated suitability as biological alkylating agents such as radio mimetic compounds as well as for the preparation of crosslinked polymers of basic ion exchange properties.

It is understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

What is claimed is:

1. An aziridine sulfonamide compound of the structural formula wherein R R R R and R are each selected from the group consisting of hydrogen and alkyl from 1 to 4 carbon atoms,

R and R are each selected from the group consisting of hydrogen, alkyl from 1 to 8 carbon atoms, alkenyl from 2 to 3 carbon atoms, monohydroxy substituted alkyl from 1 to 6 carbon atoms, phenyl, halogen-substituted phenyl, and methyl substituted phenyl.

2. 2-(l-aziridinyl)ethane sulfonamide of the formula:

\ /NCH:CH3SONH; H2

3. N-methyl-2(1-aziridinyl)ethane sulfonamide of the formula:

4. N,N-dimethyl-2-( l-aziridinyl)ethane sulfonamide of the formula:'

CH2 CH3 NCHzCHz s oiN C \CH3 9 10 5. N,N'-dia1ly1-2-(l-aziridinyDethane sulfonamide of Reference Cited the formula: FOREIGN PATENTS E, /CH CH=CHz 849,407 9/1952 Germany 2 NCHICHR S 02N L \CHCECH 5 ALTON D. ROLLINS, Primary Examiner 6. N-phenyl-Z-aziridinyl ethane sulfonamide of the fors. 1 R mula: 2602 N 

